Development and validation of a gas chromatography-tandem mass spectrometry analytical method for the monitoring of ultra-traces of priority substances in surface waters

Document Type : Research Paper

Authors

ARPA Lazio, Regional Agency for Environmental Protection; via G. Saredo 52, 00173 Rome, Italy

Abstract

The 2013/39/EU Directive of the European Parliament provided a list of substances (organic and inorganic compounds); these so-called priority and dangerous priority substances affect the quality status of surface waters. Due to their high level of toxicity, these contaminants have legal limits in the order of µg/L and even some in the order of ng/L and pg/L. To this aim, an effective and sensitive analytical method for monitoring these contaminants was deemed necessary. In this experimental process, a highly effective workflow represented by a pre-analytical and an analytical phase was developed and validated. The pre-analytical phase comprises a liquid-liquid microextraction and a quick, easy, cheap, effective, rugged, and safe purification. The analytical part was performed by a very sensitive and robust multi-residual GC-MS/MS method without the need for derivatization. This method simultaneously identified and quantified most of these substances (represented by pesticides, chloroalkane hydrocarbons, and polycyclic aromatic hydrocarbons) at very low concentration levels while respecting the analytical concentration limits required by the European directive.

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Main Subjects


[1] European Water Charter Proclaimed in Strasbourg MAY 6, 1968 (1969). https://doi.org/10.1111/j.1752-1688.1969.tb04880.x
[2] Alavanja, M.C., Hoppin, J.A., Kamel, F. (2004). Health effects of chronic pesticide exposure: cancer and neurotoxicity. The annual review of public health, 25, 155-97.
[3] IARC monographs on the evaluation of carcinogenic risks to humans. Some flame retardants and textile chemicals, and exposures in the textile manufacturing industry (1990) vol. 48, IARC Press, Lyon, France.
[4] Glüge, J., Schinkel, L., Hungerbühler, K., Cariou, R., Bogdal, C. (2018). Environmental Risks of Medium-Chain Chlorinated Paraffins (MCCPs): A Review. Environmental science and technology, 52, 6743-6760.
[5] Geng, N., Zhang, H., Xing, L., Gao, Y., Zhang, B., Wang, F., Chen, J. (2016). Toxicokinetics of short-chain chlorinated paraffins in Sprague–Dawley rats following single oral administration. Chemosphere, 145, 106-111.
[6] Xia, D., Gao, L., Zheng, M., Li, J., Zhang, L., Wu, Y., Qiao, L. (2017). Human exposure to short-and medium-chain chlorinated paraffins via mothers’ milk in Chinese urban population. Environmental science and technology, 51(1), 608-615.
[7] Warnasuriya, G. D., Elcombe, B. M., Foster, J. R., Elcombe, C. R. (2010). A mechanism for the induction of renal tumours in male Fischer 344 rats by short-chain chlorinated paraffins. Archives of toxicology, 84(3), 233-243.
[8] Pascale, A., Laborde, A. (2020). Impact of pesticide exposure in childhood. Reviews on environmental health, 35(3), 221-227.
[9] Geng, N., Zhang, H., Zhang, B., Wu, P., Wang, F., Yu, Z., Chen, J. (2015). Effects of short-chain chlorinated paraffins exposure on the viability and metabolism of human hepatoma HepG2 cells. Environmental science and technology, 49(5), 3076-3083.
[10] Oliveira, M., Slezakova, K., Delerue-Matos, C., Pereira, M. C., Morais, S. (2019). Children environmental exposure to particulate matter and polycyclic aromatic hydrocarbons and biomonitoring in school environments: a review on indoor and outdoor exposure levels, major sources and health impacts. Environment international, 124, 180-204.
[11] Fiedler, H. (2010). Short-chain chlorinated paraffins: production, use and international regulations. In Chlorinated paraffins (pp. 1-40). Springer, Berlin, Heidelberg.
[12] Huang, H., Gao, L., Xia, D., Qiao, L. (2017). Bioaccumulation and biomagnification of short and medium chain polychlorinated paraffins in different species of fish from Liaodong Bay, North China. Scientific reports, 7(1), 1-9.
[13] Liu, L., Li, Y., Coelhan, M., Chan, H. M., Ma, W., Liu, L. (2016). Relative developmental toxicity of short-chain chlorinated paraffins in Zebrafish (Danio rerio) embryos. Environmental pollution, 219, 1122-1130.
[14] Tsunemi, K. (2010). Risk assessment of short-chain chlorinated paraffins in Japan. In: Boer J. (Eds) Chlorinated paraffins. The handbook of environmental chemistry, vol 10. Springer, Berlin, Heidelberg, pp. 155-194.
[15] Li, Y.F., Macdonald, R.W. (2005). Sources and pathways of selected organochlorine pesticides to the Arctic and the effect of pathway divergence on HCH trends in biota: a review. Science of the total environment. 342, 87-106.
[16] Jones, K. C., De Voogt, P. (1999). Persistent organic pollutants (POPs): state of the science. Environmental pollution, 100(1-3), 209-221.
[17] Wania, F., Mackay, D. (1996). Peer reviewed: tracking the distribution of persistent organic pollutants. Environmental science and technology, 30(9), 390A-396A.
[18] Ogata, Y., Takada, H., Mizukawa, K., Hirai, H., Iwasa, S., Endo, S., Thompson, R. C. (2009). International Pellet Watch: Global monitoring of persistent organic pollutants (POPs) in coastal waters. 1. Initial phase data on PCBs, DDTs, and HCHs. Marine pollution bulletin, 58(10), 1437-1446.
[19] European Parliament (2000). Establishing a framework for community action in the field of water policy. Directive EC/2000/60. EU, Brussels, Belgium.
[20] Barco‐Bonilla, N., Plaza‐Bolaños, P., Tarifa, N. M. V., Romero‐González, R., Martínez Vidal, J. L., Frenich, A. G. (2014). Highly sensitive determination of polybrominated diphenyl ethers in surface water by GC coupled to high‐resolution MS according to the EU Water Directive 2008/105/EC. Journal of separation science, 37(1-2), 69-76.
[21] Amendola, L., Cortese, M., Vinatoru, D., Sposato, S., Insogna, S. (2017). Innovative analytical method for the determination of underivatized tributyltin and pentachlorophenol in seawater by gas chromatography-triple quadrupole mass spectrometry. Analytica chimica acta, 975, 70-77.
[22] Zencak, Z., Borgen, A., Reth, M., Oehme, M. (2005). Evaluation of four mass spectrometric methods for the gas chromatographic analysis of polychlorinated n-alkanes. Journal of chromatography A, 1067(1-2), 295-301.
[23] Tölgyessy, P., Nagyová, S., Sládkovičová, M. (2017). Determination of short chain chlorinated paraffins in water by stir bar sorptive extraction–thermal desorption–gas chromatography–triple quadrupole tandem mass spectrometry. Journal of chromatography A, 1494, 77-80.
[24] van Mourik, L. M., Gaus, C., Leonards, P. E., de Boer, J. (2016). Chlorinated paraffins in the environment: A review on their production, fate, levels and trends between 2010 and 2015. Chemosphere, 155, 415-428.
[25] Feo, M. L., Eljarrat, E., Barceló, D. (2009). Occurrence, fate and analysis of polychlorinated n-alkanes in the environment. Trends in analytical chemistry, 28(6), 778-791.
[26] The European parliament and council, regulation (EC) No 850/2004 on persistent organic pollutants and amending directive 79/117/EEC: Reg (EC) 850/2004.